Domino reactions of thiopyrano[4,3-b]indole-3(5H)-thiones and dimethyl acetylenedicarboxylate: Quantum chemical investigation and experiment

IF 2.1 3区化学 Q3 CHEMISTRY, MULTIDISCIPLINARY

Journal of Sulfur Chemistry Pub Date : 2023-04-01 DOI:10.1080/17415993.2022.2139147

Konstantin F. Suzdalev , Julia V. Gazizova , Valery V. Tkachev , Mikhail E. Kletskii , Anton V. Lisovin , Oleg N. Burov , Dmitriy V. Steglenko , Sergey V. Kurbatov , Gennadii V. Shilov

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引用次数: 1

Abstract

Reaction of thiopyrano[4,3-b]indole-3(5H)-thiones and dimethyl acetylenedicarboxylate (DMAD) proceeds via two competing cascade pathways. Initially, both the pathways begin from thiocarbonyl sulfur and acetylene carbon atoms interaction. Then two parallel processes take place: an alkyne–thiocarbonyl metathesis and a (3 + 2) cycloaddition. In the next stages, in both cases, thiophene ring formation and thiopyran ring opening proceed. Finally, (4 + 2) cycloaddition reactions of intermediate thioketones and a second equivalent of DMAD leads to the resulting thiopyrano[4,3-b]indole derivatives bearing thienyl substituent. The kinetic and thermodynamic characteristics of both pathways were compared on the basis of DFT and ab initio 6-311++G(d,p) quantum chemical calculations.

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硫代吡喃并[4,3-b]吲哚-3（5H）-硫酮与乙炔二羧酸二甲酯的Domino反应：量子化学研究与实验

硫代吡喃[4,3-b]吲哚-3(5H)-硫酮与二甲基乙酰二羧酸酯(DMAD)的反应通过两个相互竞争的级联途径进行。最初，这两种途径都是从硫羰基硫和乙炔碳原子相互作用开始的。然后发生两个平行过程:炔-硫羰基复分解和(3 + 2)环加成。在接下来的阶段，在这两种情况下，硫噻吩环形成和硫吡喃环开环进行。最后，中间体硫酮和第二等价物DMAD的(4 + 2)环加成反应得到含噻基取代基的硫代吡喃[4,3-b]吲哚衍生物。基于DFT和从头算6-311++G(d,p)量子化学计算，比较了两种途径的动力学和热力学特性。图形抽象

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来源期刊

Journal of Sulfur Chemistry CHEMISTRY, MULTIDISCIPLINARY-

CiteScore

4.10

自引率

9.10%

发文量

审稿时长

6-12 weeks

期刊介绍： The Journal of Sulfur Chemistry is an international journal for the dissemination of scientific results in the rapidly expanding realm of sulfur chemistry. The journal publishes high quality reviews, full papers and communications in the following areas: organic and inorganic chemistry, industrial chemistry, materials and polymer chemistry, biological chemistry and interdisciplinary studies directly related to sulfur science. Papers outlining theoretical, physical, mechanistic or synthetic studies pertaining to sulfur chemistry are welcome. Hence the target audience is made up of academic and industrial chemists with peripheral or focused interests in sulfur chemistry. Manuscripts that truly define the aims of the journal include, but are not limited to, those that offer: a) innovative use of sulfur reagents; b) new synthetic approaches to sulfur-containing biomolecules, materials or organic and organometallic compounds; c) theoretical and physical studies that facilitate the understanding of sulfur structure, bonding or reactivity; d) catalytic, selective, synthetically useful or noteworthy transformations of sulfur containing molecules; e) industrial applications of sulfur chemistry; f) unique sulfur atom or molecule involvement in interfacial phenomena; g) descriptions of solid phase or combinatorial methods involving sulfur containing substrates. Submissions pertaining to related atoms such as selenium and tellurium are also welcome. Articles offering routine heterocycle formation through established reactions of sulfur containing substrates are outside the scope of the journal.